Acid dye mixture

ABSTRACT

The present invention refers to a red-dyeing acid dye mixture comprising a dye of the formula (I) 
                         
and at least one dye of the formula (II)
 
                         
a process for its manufacturing and a process for dyeing and printing of natural or synthetic polyamide fiber material in which it used.

RELATED APPLICATIONS

This application claims benefit under 35 U.S.C. 119(e) to Ser. No.60/650,475, filed Feb. 7, 2005.

The present invention relates to the field of acid dyes. Acid dyes areknown and can be used for dyeing and printing of natural and syntheticpolyamide fiber material.

The documents U.S. Pat. No. 4,537,598, U.S. Pat. No. 5,090,964, U.S.Pat. No. 5,131,919 and U.S. Pat. No. 6,443,998 describe mixtures ofred-dyeing acid dyes, which can also be used for dyeing and printing ofpolyamide fiber and which are suitable for combination dyeing by thetrichromatic technique.

However, the known dyes and dyestuff mixtures, respectively, have somedisadvantages as regards applicability in the dyehouse as well asregards fastness properties of the dyed material.

It is an object of the present invention to provide improved red-dyeingmixtures of acid dyes which are suitable for dyeing or printing ofnatural or synthetic polyamide fiber material from an aqueous bath andshow good exhaustion especially in combination with other dyes, inparticular from short liquors and have very good levelling and fastnessproperties especially light fastness properties.

The present invention relates to a dye mixture comprising a dye of theformula (I)

wherein M is hydrogen, an alkali metal, an ammonium ion or theequivalent of an alkaline earth metal,

and at least one dye of the formula (II)

wherein

R¹ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₈)-alkyl which is substituted byhalogen, halogen, benzoylamino, benzoylamino, which is substituted inthe phenyl ring by halogen, —SO₂-phenyl, —SO₂-phenyl, which issubstituted in the phenyl ring by (C₁-C₈)-alkyl, —SO₂—O-phenyl,1-azacycloheptan-N-sulfonyl, or a group of the formula (III)

in which R⁴ is (C₁-C₈)-alkyl, (C₃-C₈)-cycloalkyl, phenyl or phenyl whichis substituted by (C₁-C₈)-alkyl and R⁵ is hydrogen or (C₁-C₈)-alkyl;

R² is hydrogen, halogen, (C₁-C₈)-alkyl or a group of the formula (IV)

wherein R⁶ is hydrogen, methyl or ethyl; and R⁷ is (C₁-C₆)-alkyl, phenylor —CO—O—(C₃-C₈)-cycloalkyl

R³ is hydrogen, halogen or (C₁-C₈)-alkyl;

M is hydrogen, an alkali metal, an ammonium ion or the equivalent of analkaline earth metal,

whereas formula (II) does not include a dye of formula (I) and

whereas mixtures comprising a dye of the formula (I) and a dye of theformula (II), wherein R¹ is trifluoromethyl and R² and R³ are bothhydrogen and a dye of the formula (II), wherein R¹ is a group of theformula (III) in which R⁴ is cyclohexyl and R⁵ is methyl and R² and R³are both hydrogen, are excluded and

whereas mixtures consisting of the dye of the formula (I) and a dye ofthe formula (II), wherein R¹ is trifluoromethyl and R² and R³ are bothhydrogen, are excluded.

(C₁-C₈)-alkyl groups may be straight-chain or branched and are forexample methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl,tert.-butyl, pentyl, hexyl, heptyl or octyl. Preferred are (C₁-C₄)-alkylgroups, like methyl, ethyl, n-propyl and n-butyl.

(C₃-C₈)-cycloalkyl is preferably cyclohexyl.

Halogen is preferred fluorine, chlorine and bromine. Accordingly, a(C₁-C₈)-alkyl group, which is substituted by halogen is preferablysubstituted by fluorine, chlorine or bromine. An especially preferred(C₁-C₈)-alkyl group, which is substituted by halogen, istrifluoromethyl.

Halogen standing for R² or R³ is preferably fluorine, chlorine andbromine and especially preferred chlorine.

A substituted phenyl group standing for R⁴ is preferred substituted bymethyl.

M is preferably hydrogen, sodium or potassium.

Preferred dyes of the formula (II) are the dyes of the formulae (IIa) to(IIp)

wherein M is defined as given above.

A preferred dye mixture comprises a dye of the formula (I) and a dye ofthe formula (IIa) or a dye of the formula (IIm).

Another preferred dye mixture consists of a dye of the formula (I) and adye of the formula (IIa) or a dye of the formula (IIm).

Still another preferred dye mixture comprises a dye of the formula (I)and at least two dyes of the formula (II), one of which is a dye of theformula (IIb).

Still another preferred dye mixture comprises a dye of the formula (I)and a dye of the formula (IIa) and a dye of the formula (IIb) or (IIm).

The dye mixtures according to the present invention contain the dye ofthe formula (I) preferably in amounts of 5 to 95% by weight and the dyeor the dyes of the formula (II) preferably in amounts of 95 to 5% byweight. The dye mixtures according to the present invention contain thedye of the formula (I) especially preferably in amounts of 40 to 80% byweight and the dye or the dyes of the formula (II) especially preferablyin amounts of 60 to 20% by weight.

The present invention also relates to dye mixtures which comprise 90 to99.99% by weight of a dye mixture comprising a dye of the formula (I)and at least one dye of the formula (II) and 10 to 0.01% by weight ofone or more shading agents.

Shading agents are dyes which can be used to modify the shade of theinventive dye mixtures in order to adjust it to a certain shadestandard.

Preferred shading agents are acid dyes of yellow, orange or blue coloror other dyes of yellow, orange or blue color which can be used togetherwith the inventive dye mixture.

Especially preferred shading agents are the yellow, orange and blue dyesmentioned below.

The present invention also relates to a process for the manufacturing ofthe dye mixture of the present invention, which comprises mechanicalmixing of the dye of the formula (I) and the dye or the dyes of theformula (II) in the required amounts. The dyes of the formulae (I) and(II) are known and can be purchased at the market place or produced inline with methods known to those skilled in the art.

The dye mixtures of the present invention are suitable for dyeing andprinting of natural or synthetic polyamide fiber material by theapplication methods numerously described in the art for acid dyes.Therefore, the present invention also relates to a process for dyeingand printing of natural or synthetic polyamide fiber material in which adye mixture according to the present invention is used.

A preferred natural polyamide fiber material is wool, whereas preferredsynthetic polyamide fiber materials are nylon materials, like nylon-6and nylon-6.6.

The inventive dye mixtures are especially suitable for combinationdyeing by the trichromatic technique. According to this method, theinventive red-dyeing mixtures are used together or in mixture withsuitable blue-dyeing dyes or dye mixtures and suitable yellow- ororange-dyeing dyes or dye mixtures.

Therefore, the present invention also relates to a process fortrichromatic dyeing and printing of natural or synthetic polyamide fibermaterial in which a dye mixture according to the present invention isused, together with at least one blue-dyeing dye or dye mixture and atleast one yellow- or orange-dyeing dye or dye mixture.

Preferred blue-dyeing dyes are the dyes of the formula (IIIa)

wherein R⁸ is methyl or ethyl and M is defined as given above.

Preferred dyes of the formula (IIIa) are the dyes of the formulae (IIIb)and (IIIc)

Other preferred blue-dyeing dyes are the dyes of the formulae (IIId) to(IIIh)

wherein M is defined as given above and mixtures of two or more dyes ofthe formulae (IIIa) to (IIIh).

Preferred yellow- or orange-dyeing dyes are the dyes of the formulae(IVa) to (IVh)

wherein M is defined as given above and mixtures of two or more dyes ofthe formulae (IVa) to (IVh).

A preferred yellow- or orange-dyeing mixture a mixture comprising a dyeof the formula (IVa) and a dye of the formula (IVi)

wherein M is defined as given above.

The mixture comprising a dye of the formula (IVa) and a dye of theformula (IVi) contain the dye of the formula (IVa) preferably in amountsof 5 to 95% by weight and the dye of the formula (IVi) preferably inamounts of 95 to 5% by weight. Especially preferred are 40 to 60% byweight of a dye of the formula (IVa) and 60 to 40% by weight of a dye ofthe formula (IVi).

Using usual exhaust or continuous dyeing and printing techniques, whichare known to a person skilled in the art, the inventive dye mixtureshows improved on-tone build-up in combination with a blue-dyeing dyeand/or a yellow- or orange dyeing dye or dye mixture thereof.

On critical fiber material, e.g. high-delustered, pre-heatsettedmicro-fibers, the present invention shows improved light fastness due toon-tone fading.

Example 1

To prepare a dye mixture comprising a dye of the formula (I) and a dyeof the formula (IIa), 60 parts of the dye of the formula (I) in form ofits sodium salt and 40 parts of the dye of the formula (IIa) in form ofits sodium salt are mixed homogeneously to give 100 parts of the dyemixture which hereafter is called mixture A.

Example 2

To prepare a dye mixture comprising a dye of the formula (I) and a dyeof the formula (IIm), 25 parts of the dye of the formula (I) in form ofits sodium salt and 75 parts of the dye of the formula (IIm) in form ofits sodium salt are mixed homogeneously to give 100 parts of the dyemixture which hereafter is called mixture B.

Example 3

To prepare a dye mixture comprising a dye of the formula (I), a dye ofthe formula (IIa) and a dye of the formula (IIb), 50 parts of the dye ofthe formula (I) in form of its sodium salt, 40 parts of the dye of theformula (IIa) in form of its sodium salt and 10 parts of the dye of theformula (IIb) in form of its sodium salt are mixed homogeneously to give100 parts of the dye mixture which hereafter is called mixture C.

Example 4

10 parts of a nylon-6,6 material (Helanca fabric) are dyed in 200 partsof an aqueous solution containing 2 g/l ammonium acetate and having apH-value of 5 which has been adjusted with acetic acid. The dyes thatare used are 0.10% of the red dyeing mixture A according to Example 1,0.15% of a orange dyeing dyestuff mixture comprising equimolar amountsof the dye of the formula (IVa) and the dye of the formula (IVi) and0.12% of the blue-dyeing dye of the formula (IIIb), the amounts givenbeing based on the weight of the Helanca fabric. All dyes were used inform of their sodium salts.

The dyeing time at a temperature of 60 to 90° C. is 30 to 90 minutes.After that, the dyed nylon-6,6 fabric is removed from the liquor, rinsedand dried as usual. This gives a piece of fabric completely levelly dyedin a brown shade having no material-related streaks whatever and highlight fastness properties.

Examples 5 to 11

Example 4 is repeated with the difference that the dyes and dyemixtures, respectively, and the amounts given in the following tablewere used. All dyeings obtained were completely level and with highlight fastness properties.

Example Dyes used Shade 5 0.035% of an equimolar mixture of the dyeslight grey of formulae (IVa) and (IVi) 0.023% of Mixture A 0.063% of thedye of the formula (IIIb) 6 0.060% of an equimolar mixture of the dyesolive of formulae (IVa) and (IVi) 0.005% of Mixture A 0.075% of the dyeof the formula (IIIb) 7 0.021% of an equimolar mixture of the dyes brownof formulae (IVa) and (IVi) 0.027% of Mixture A 0.020% of the dye of theformula (IIIb) 8 0.035% of an equimolar mixture of the dyes light greyof formulae (IVa) and (IVi) 0.023% of Mixture B 0.063% of the dye of theformula (IIIb) 9 0.021% of an equimolar mixture of the dyes brown offormulae (IVa) and (IVi) 0.027% of Mixture B 0.020% of the dye of theformula (IIIb) 10 0.035% of an equimolar mixture of the dyes light greyof formulae (IVa) and (IVi) 0.023% of Mixture C 0.063% of the dye of theformula (IIIb) 11 0.021% of an equimolar mixture of the dyes brown offormulae (IVa) and (IVi) 0.027% of Mixture C 0.020% of the dye of theformula (IIIb)

The invention claimed is:
 1. A dye mixture comprising a dye of theformula (I)

wherein M is hydrogen, an alkali metal, an ammonium ion or theequivalent of an alkaline earth metal, and at least one dye of theformula (IIa) or (IIb)

M is defined above, and at least one dye of the formula (IIIc), (IIId),(IIIe) or (IIIg)

wherein M is defined above.
 2. The dye mixture according to claim 1,wherein M is hydrogen, sodium or potassium.
 3. A process for themanufacturing of the dye mixture according to claim 1, which comprisesmechanical mixing of the dye of the formula (I) and the dye or the dyesof the formula (IIa) or (IIb) and at a dye of the formula (IIIc),(IIId), (IIIe) or (IIIg).
 4. A process for dyeing and printing ofnatural or synthetic polyamide fiber material which comprises applyingsaid dye mixture according to claim 1 to said material.
 5. A process fortrichromatic dyeing and printing of natural or synthetic polyamide fibermaterial which comprises applying to said material said dye mixtureaccording to claim 1 together with at least one blue-dyeing dye or dyemixture and at least one yellow- or orange-dyeing dye or dye mixture. 6.The process according to claim 5, wherein a dye selected from the groupconsisting of the dyes of formulae (IVa) to (IVh)

wherein M is hydrogen, an alkali metal, an ammonium ion or theequivalent of an alkaline earth metal, or mixtures of two or more dyesof the formulae (IVa) to (IVh) are used as yellow- or orange dyeing dye.7. The process according to claim 6, wherein a mixture of a dye of theformula (IVa) and a dye of the formula (IVi)

wherein M is hydrogen, an alkali metal, an ammonium ion or theequivalent of an alkaline earth metal, is used as yellow or orangedyeing dye.
 8. The dye mixture as claimed in claim 1, which furthercomprises at least one dye selected from the group consisting of thedyes of formulae (IVa) to (IVh)

wherein M is hydrogen, an alkali metal, an ammonium ion or theequivalent of an alkaline earth metal.
 9. The dye mixture as claimed inclaim 8, wherein at least one dye of the formula (IVb), (IVd), (IVe) or(IVf) is used and at least one of the dyes of the formula (IIId), (IIIe)or (IIIg) is used.
 10. The dye mixture according to claim 1, consistingof the dye of the formula (I), the dye of the formulas (IIa) or (IIb) orthe dye of formula (IIa) and (IIb) and at least one dye of the formula(IIIc), (IIId), (IIIe) or (IIIg) and optionally comprises at least onedye selected from the group consisting of the dyes of formulae (IVa) to(IVh)

wherein M is hydrogen, an alkali metal, an ammonium ion or theequivalent of an alkaline earth metal.
 11. A dye mixture comprising adye of the formula (I)

wherein M is hydrogen, an alkali metal, an ammonium ion or theequivalent of an alkaline earth metal, and at least one dye of theformula (IIa) or (IIb)

M is defined above, and at least one dye of the formula (IVb), (IVd),(IVe) or (IVf)

wherein M is defined above.
 12. The dye mixture as claimed in claim 11,which further comprises at least one dye selected from the groupconsisting of the dyes of formulae (IIIb) to (IIIh)

wherein M is hydrogen, an alkali metal, an ammonium ion or theequivalent of an alkaline earth metal.
 13. The dye mixture as claimed inclaim 12, wherein a dye of the formula (IIIc), (IIId)., (IIIe) or (IIIg)is used.
 14. The dye mixture according to claim 11, wherein M ishydrogen, sodium or potassium.
 15. A process for the manufacturing ofthe dye mixture according to claim 11, which comprises mechanical mixingof the dye of the formula (I) and the dye or the dyes of the formula(IIa) or (IIb) and at least one dye of the formula (IVb), (IVd), (IVe)or (IVf).
 16. A process for dyeing and printing of natural or syntheticpolyamide fiber material which comprises applying said dye mixtureaccording to claim 11 to said material.
 17. A dye mixture consisting ofa dye of the formula (I)

wherein M is hydrogen, an alkali metal, an ammonium ion or theequivalent of an alkaline earth metal, and at least one dye of theformula (IIa) or (IIb)

M is defined above, and only one dye selected from the group consistingof the dyes of formulae (IIIb) to (IIIh)

and optionally at least one dye selected from the group consisting ofthe dyes of formulae (IVa) to (IVh)

wherein M is defined above.
 18. The dye mixture as claimed in claim 17,wherein the dye of the formula dye of the formula (IIIc), (IIId), (IIIe)or (IIIg) is used.
 19. The dye mixture as claimed in claim 17, whereinthe dye of the formula dye of the formula (IVb), (IVd), (IVe) or (IVf)is used.
 20. A process for dyeing and printing of natural or syntheticpolyamide fiber material which comprises applying said dye mixtureaccording to claim 17 to said material.
 21. A dye mixture consisting ofa dye of the formula (I)

wherein M is hydrogen, an alkali metal, an ammonium ion or theequivalent of an alkaline earth metal, and at least one dye of theformula (IIa)

M is defined above, and only one dye selected from the group consistingof the dyes of formulae (IIIb) to (IIIh)

and optionally at least one dye selected from the group consisting ofthe dyes of formulae (IVa) to (IVh)

wherein M is defined above.
 22. The dye mixture as claimed in claim 21,wherein the dye of the formula (IIIc), (IIId), (IIIe) or (IIIg) is used.23. The dye mixture as claimed in claim 21, wherein the dye of theformula (IVb), (IVd), (IVe) or (IVf) is used.
 24. A process for dyeingand printing of natural or synthetic polyamide fiber material whichcomprises applying said dye mixture according to claim 21 to saidmaterial.